CN105980471A - Thermoplastic polyolefin with reduced gloss for non-carpeted flooring - Google Patents

Thermoplastic polyolefin with reduced gloss for non-carpeted flooring Download PDF

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Publication number
CN105980471A
CN105980471A CN201580007911.XA CN201580007911A CN105980471A CN 105980471 A CN105980471 A CN 105980471A CN 201580007911 A CN201580007911 A CN 201580007911A CN 105980471 A CN105980471 A CN 105980471A
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branched
ethylene
weight portions
weight
olefin
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CN105980471B (en
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J·T·塞利斯卡
J·D·厄尔贝格
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Dow Global Technologies LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60N—SEATS SPECIALLY ADAPTED FOR VEHICLES; VEHICLE PASSENGER ACCOMMODATION NOT OTHERWISE PROVIDED FOR
    • B60N3/00—Arrangements or adaptations of other passenger fittings, not otherwise provided for
    • B60N3/04—Arrangements or adaptations of other passenger fittings, not otherwise provided for of floor mats or carpets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/08—Low density, i.e. < 0.91 g/cm3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/17—Viscosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
    • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/064—VLDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/07—Long chain branching

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  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Transportation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)

Abstract

The present invention is directed to an elastomer composition comprising an ethylene/alpha-olefin/diene modified interpolymer, a very low density polyethylene component, and a propylene polymer component, wherein the propylene polymer component comprises at least one branched polypropylene. The inventive compositions are particularly suitable for fabricating thermoformed non-carpet automotive flooring.

Description

The TPO of the glossiness with reduction on floor for not carpeting
Technical field
The present invention relates to the thermoplastic polyolefin composition applied for non-carpet floor, it comprises one or more linear second Alkene polymer and/or the polymer of substantial linear, polypropylene and ethylene propylene diene monomer rubber.Especially, thermoplastic Property polyolefin composition there is the well balanced of melt strength and percentage elongation so that it is particularly suitable for sheet material extrusion and subsequently Hot forming, for having the truck of glossiness and the application of automobile non-carpet floor of reduction.
Background technology
Automaker requires that the flooring material do not carpeted has good wearability, scoring resistance and marresistance, low Glossiness and texture definition, simultaneously pigmentable, durable and big temperature can be born change without occurring damaging. Additionally, automaker requires that flooring material has low modulus (elastic), in order to be installed in vehicle.
Known to the flooring material do not carpeted can (part be handed over by impact-resistant modified polypropylene and high melt strength, propylene Connection) blend manufacture.Impact-resistant modified polypropylene produces flexible so that being installed in vehicle and facilitating low-luster, And high melt strength, propylene is conducive to scoring resistance and marresistance, and during heat forming processes, provide enough strong Degree.But, flooring material known to these has narrow temperature range window for hot forming.The high-crystallinity of material is led Cause the drastically decline of melt strength during heat forming processes.Additionally, along with forming temperature increases, floor known to these The glossiness of material also significantly increases, and this is unsatisfactory for automaker's requirement.
Have been developed for maintaining the TPO for low-luster sheet material (TPO) compositions of low-luster, The automobile application of the glossiness for reducing.In order to prepare manufacture goods or product (such as, instrument board, door-plate and not The floor carpeted) one or more ethylene/alpha-olefin olefin elastomers and one or more polyacrylic TPO blends be Known.See for example USP 6,372,847；6,680,361；7,750,104；8,304,496；And 8,431,651. These blends and product show many desired qualities, such as, good to excellent melt strength and machinability, Moldability, shock resistance and marresistance, modulus, elasticity etc..But, some are applied, these TPO compositionss Acceptable gloss level is provided unsuitable for hot forming and/or for manufacture goods prepared therefrom.
It is desirable that, have the elastic composition that thermoformable is the floor applications do not carpeted, it has the resistance to of improvement Mill property, the glossiness of reduction and low abnormal smells from the patient and low emission.
Summary of the invention
The present invention is this type of elastic composition.It is 40 weight portions second to 60 weight portions that described compositions comprises a) amount The interpretation that alkene/alpha-olefin/diene is modified, it has the density of 0.84g/cc to 0.92g/cc and as according to ASTM D 1646 Mooney viscosities (Mooney viscosity) at 125 DEG C equal to or more than 50ML (1+4) measured；b) Amount is 10 weight portions ethylene polymer component to 20 weight portions, and its density equals to or less than 0.89g/cc；And c) Amount is 20 weight portions propylene polymer component to 30 weight portions, and it comprises at least one branched p 0 lypropylene.
In one embodiment, the present invention is elastic composition disclosed above, and wherein ethylene/alpha-olefin/diene changes The interpretation of property is 5-ethylidene-2-norbornene；1,4-hexadiene；Or 7-methyl isophthalic acid, 6-octadiene.
In one embodiment, the present invention is elastic composition disclosed above, at least one of which branched p 0 lypropylene For propylene and the copolymer of alpha-olefin, described alpha-olefin selected from ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene or 1-octene, preferably propylene polymer component are branched p 0 lypropylene and unbranched polyacrylic mixture, and more preferably In terms of the weight of propylene polymer component, branched p 0 lypropylene exists with at least 50 weight %.
In another embodiment, the present invention is a kind of method preparing the floor that automobile use is not carpeted, described method bag Containing following steps: i) form the sheet material comprising elastic composition disclosed above and ii) this sheet material is thermoformed into vapour The automobile-used floor do not carpeted.
In another embodiment, the present invention is method as described above, wherein sheet material be AB type coextrusion sheet material or ABA type coextrusion sheet material, wherein comprising elastomer compositions is A layer.
In another embodiment, the present invention is a kind of goods comprising elastic composition disclosed above, preferably The automobile floor do not carpeted.
Detailed description of the invention
Ethylene/alpha-olefin (EAO) component (a) of elastic composition of the present invention comprises at least one and optionally can contain The ethylene/alpha-olefin interpolymers of diene.For example, USP 8 is seen, 304,496, entire contents is incorporated herein. As used herein, " interpretation " refers to wherein be polymerized the polymer of at least two monomer.It include such as copolymer, Terpolymer and quadripolymer.It especially includes for preparing by being polymerized with at least one comonomer by ethylene gathers Compound, described comonomer is usually 3 to 20 carbon atoms (C3-C20), more preferably 3 to 12 carbon atoms (C3-C12) and the even more preferably still alhpa olefin (alpha-olefin) of 3 to 8 carbon atoms (C3-C8).Illustrative α- Alkene includes propylene, 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, butadiene and benzene Ethylene.Alpha-olefin is preferably C3-C10 alpha-olefin.
Illustrative polymer includes ethylene/propene (EP) copolymer, ethylene/butylene (EB) copolymer, ethylene/octene (EO) The interpretation of copolymer, ethylene/alpha-olefin/diene modified (EAODM) is (as ethylene/propylene/diene is modified (EPDM) Interpretation) and ethylene/propylene/octene terpolymer.Preferably copolymer includes EP, EB, ethylene/1-hexene (EH) With EO polymer.
Preferably, the EAO for the present invention is the interpretation that ethylene/alpha-olefin/diene is modified.Suitably diene monomers bag Include conjugated diene and non-conjugated diene.Non-conjugated diene hydrocarbon is routinely by the cure site acting on crosslinking.Non-conjugated diene Hydrocarbon can be C6-C15 straight chain, side chain or cyclic hydrocarbon diene.Illustrative non-conjugated diene includes straight chain acyclic diene, as Isosorbide-5-Nitrae- Hexadiene and 1,5-heptadiene；Branched non cyclic diene, such as 5-methyl isophthalic acid, 4-hexadiene, 2-methyl isophthalic acid, 5-hexadiene, 6- Methyl isophthalic acid, 5-heptadiene, 7-methyl isophthalic acid, 6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,5-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene, 1,9-decadinene and the mixed isomers of dihydromyrcene；Single ring alicyclic dienes, as 1,4-cyclohexadiene, 1,5-cyclo-octadiene and 1,5-ring 12 diene；Multi-ring alicyclic condense and bridging cyclic diolefine, such as tetrahydrochysene Indenes, methyl tetrahydroindene；Thiazolinyl, alkylidene, cycloalkenyl group and cycloalkylidene norborene, such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norborene, 5-acrylic-2-norborene, 5-isopropylidene-2-norborene, 5-(4-cyclopentenyl)-2-norborene and 5-cyclohexylidene-2-norborene.Diene is excellent Elect free ENB, Isosorbide-5-Nitrae-hexadiene, 7-methyl isophthalic acid, the non-conjugated diene of the group of 6-octadiene composition, more preferably ENB as.
Suitably conjugated diene includes 1,3-pentadiene, 1,3-butadiene, 2-methyl isophthalic acid, 3-butadiene, 4-methyl isophthalic acid, 3-penta 2 Alkene or 1,3-cyclopentadiene.Though EAODM diene monomers comprise conjugated diene, non-conjugated diene or both, its Content all falls in the restriction specified above of non-conjugated diene.
Although preferably interpretation is substantially free of the diene monomers of any usual initiation long chain branching (LCB), but such as Really the acceptable and desired interpretation characteristic (such as machinability, hot strength and percentage elongation) of cost will not be reduced to Unacceptable level, then this type of monomer can be included.This type of diene monomers includes bicyclopentadiene, NBD, methyl Norbornadiene, vinyl norbornene, 1,6-octadiene, 1,7-octadiene and 1,9-decadinene.Add when adding this type of monomer Time, in terms of interpretation weight, this type of monomer generally with more than 0 to 3 weight %, more preferably greater than 0 to 2 weight % models Enclose interior amount to add.
The EAO interpretation of the present invention can comprise branched or unbranched ethylene/alpha-olefin interpolymers, or two or more Change and/or the blend of unbranched interpretation.Presence or absence branched in ethylene/alpha-olefin interpolymers, and such as Fruit exists branched, then branched amount can be extensively varied, and is heavily dependent in thermo shaping method and blend The amount of branched p 0 lypropylene.Use formpiston (such as, for pattern is applied to a piece of smooth plastics prepared by blend On cylinder) thermo shaping method preferably medium branched to highly branched ethylene/alpha-olefin interpolymers by one or more Plastic sheet is formed with the compositions of branched p 0 lypropylene.
The practice of the present invention is not critical to by the character of ethylene/alpha-olefin (EAO) branched (if present), And therefore it can change according to convenience.Preferably, Zhi Huawei LCB.LCB is incorporated in main polymer chain Ability is known and has applied many years.At USP 3, in 821,143, Isosorbide-5-Nitrae-hexadiene is used as branched monomer system Get everything ready ethylene/propylene/diene (EPDM) polymer of LCB.This type of branching agent is sometimes referred to as H branching agent.USP 6,300,451 and 6,372,847 also use various H type branching agent to prepare the polymer with LCB.At USP In 5,278,272, find that the catalyst (CGC) of constrained geometry configuration is had the ability by the macromonomer of ethenyl blocking also Enter in main polymer chain to form LCB polymer.This type of is branched be referred to as T-shaped branched.These patents (USP 3,821,143；6,300,451；6,372,847 and 5,278,272) each way of reference in full in is incorporated herein.
' 272 patent instructs this type of CGC to be only in terms of its ability being incorporated in main polymer chain by big unsaturated molecule Special.Can be 0.01LCB/1000 carbon atom to 3LCB/1000 carbon by the amount of the LCB that these CGC are incorporated to Atom.There are other methods various that can be used for limiting LCB degree in the molecule.This type of method a kind of is at USP Instruct in 6,372,847.This method uses Mooney stress relaxation data to calculate MLRA/MV ratio.MLRA is door Buddhist nun relaxes area and MV is the Mooney viscosity of polymer.Mooney viscosity is measured according to ASTM D 1646.The present invention The Mooney viscosity of EAO interpretation at 125 DEG C equal to or more than 50ML (1+4), preferably at 125 DEG C equal to or More than 60ML (1+4) and more preferably at 125 DEG C equal to or more than 70ML (1+4).
Under shear rate in the range of 0.1-100 orphan's degrees second (rad/sec) and at 190 DEG C, under nitrogen atmosphere, Use dynamical mechanical spectrometer (RMS-800 or ARES as from Lei Meiteli (Rheometrics)), 0.1 Interpretation viscosity is advantageously measured, to moor (dyne-second/square centimeter under the dynamic scan of rad/sec to 100rad/sec (d-sec/cm2)) meter.Viscosity under 0.1rad/sec and 100rad/sec can be expressed as V0.1And V100, wherein Both ratio referred to as RR and be expressed as V0.1/V100.By following formula calculating PRR:
PRR=RR+ [[3.82-interpretation Mooney viscosity (ML1+4, at 125 DEG C)] × 0.3].
In one embodiment of the invention, the PRR of EAO interpretation is 8 to 70, preferably 12 to 60, and more excellent Elect 15 to 55, and most preferably 18 to 50 as.In another embodiment, the PRR of EAO interpretation arrives for-6 70.All indivedual values and the subrange of-6 to 70 and 8 to 70 (PRR values) are all incorporated herein and are disclosed in Herein.Many current commercial EAO resins have the LCB level being equal to the PRR value less than 3.As reference Point, PRR 70 is equivalent to MLRA/MV value 7.6.
Formation branched with H type compares, and the LCB type in the interpretation used in the practice of the present invention is preferably T-shaped Change.Generally by the presence of the catalyst (metallocene-type or single site catalysts) of constrained geometry configuration, the most anti- (as in USP 6, those described in 680,361, it is incorporated herein in entirety by reference) under the conditions of answering device, will Ethylene or macromonomer undersaturated with the end of the chain combined polymerization of other alhpa olefin obtain T-shaped branched.If it is desire to extremely large water Flat LCB, then H type Zhi Huawei method for optimizing, because the T-shaped branched upper limit that LCB degree is had reality.As At USP 6, being discussed in 680,361, along with the increase of T-shaped branching level, efficiency or the volume of production of manufacturing process are notable Ground reduces, until reaching production to become the most infeasible point.T-shaped LCB polymer can be by constrained geometry configuration Catalyst prepares without measuring gel, however it is necessary that the most high-caliber T-shaped LCB.Owing to being incorporated into growth Macromonomer in polymer chain only has a unsaturated site of reaction, so resulting polymers contains only different length Side chain and at the different interval of main polymer chain.
Generally by ethylene or other alhpa olefin with have can be with two of the Nonmetallocene type catalyst reaction in polymerization It is branched that the combined polymerization of the diene of double bond obtains H type.As the name implies, diene passes through diene bridging by a polymer Molecule is connected to another polymer molecule, and resulting polymers molecule is similar to H, can be described as more cross-linking than long chain branches. When expecting high level branched, generally use H type branched.If using too many diene, then polymer molecule So many branched or crosslinking can be formed so that polymer molecule no longer dissolves in reaction dissolvent (in solwution method), And therefore separate out from solution, cause being formed in the polymer gel particle.Additionally, the use of H type branching agent can be passivated Metallocene catalyst and reduce catalyst efficiency.Therefore, when using H type branching agent, the catalyst used is usual It it not metallocene catalyst.USP 6,372,847 (being incorporated herein in entirety by reference) is used for prepare H type prop up The catalyst of fluidized polymer is vanadium type catalyst.
Lai et al., at USP 5, describes T-shaped LCB polymer in 272,236, wherein the degree of LCB is 0.01 LCB/1000 carbon atom to 3LCB/1000 carbon atom and catalyst (the cyclopentadienyl gold that catalyst is constrained geometry configuration Genotype or single site catalysts).
According to P.Doerpinghaus and D.Baird, " rheology magazine (Journal of Rheology) ", 47 (3), the 717-736 page, in May, 2003/June, " by sparse long chain branching on the impact of rheological characteristic and due to polyethylene Middle molecule Measure the impact on rheological characteristic and separate (Separating the Effects of Sparse Long-Chain Branching on Rheology from Those Due to Molecular Weight in Polyethylenes) ", free radical method is (as being used for Prepare those methods of Low Density Polyethylene (LDPE)) prepare the polymer with high horizontal LCB.
Suitably ethylene interpolymer includes being purchased from Dow Chemical (The Dow Chemical Company) ENGAGETMAnd NORDELTMPolymer；Be purchased from Exxon Mobil chemical company (ExxonMobil Chemical Company) VISTALONTMAnd EXACTTMPolymer；And it is purchased from Mitsui Chemicals (Mitsui Chemical) TAFMERTMPolymer.
In another embodiment, elastomeric component comprises coupling polymer, its by admixture is heated to poly-(sulphonyl fold Nitrogen) at least decomposition temperature, maintain be enough to decompose poly-(sulfonyl azide) of at least about 80 weight % and be enough to produce have little Preparing in the time period of the coupling polymer of about 2 weight % gel contents, described admixture contains (1) at least one bullet Gonosome, it comprises ethylene and at least one comonomer, and described comonomer is selected from the α alkene with at least 3 carbon atoms Hydrocarbon, diene and combinations thereof, and at least one poly-(sulfonyl azide) of (2) coupling amount.USP 6,376,623；6,506,848 This base polymer is described with 6,528,136；Each it is incorporated herein in entirety by reference.
The 0.1rad/sec shear viscosity (also referred to as low-shear viscosity) of the EAO interpretation used in the practice of the present invention It is typically larger than 100,000, preferably greater than 200,000.This shear viscosity is by cutting at 0.1 lonely degrees second (rad/sec) Under cutting speed rate, at 190 DEG C, under nitrogen atmosphere, use dynamical mechanical spectrometer (as from Lei Meiteli (Rheometrics) RMS-800 or ARES) measure polymer viscosity measure.Low-shear viscosity is by polymer Molecular weight (MW) and the impact of its LCB degree.Molecular weight is measured indirectly by melt strength.It is, in general, that it is poly- The molecular weight of compound is the biggest, and melt strength is the best.But, when molecular weight becomes the biggest, polymer becomes to be difficult to. LCB is incorporated in main polymer chain improve the machinability of high MW polymer.Therefore, low-shear viscosity (0.1 Rad/sec) it is the measuring of the balance of MW and LCB in polymer.
As used herein, melt strength (MS) is the maximum pull in terms of centinewton (cN), and it is with 33 Inverse (the second of second-1) constant shear rate at the melt filament of the polymer melt extruded from capillary rheometer mould Upper measurement, long filament is made long filament with 0.24 cel/second (cm/sec simultaneously2) speed from the initial speed of about 1 cel A pair roller stretching that degree accelerates.Melt filament generates the most in the following manner: 10 grams (g) is filled into Instron Polymer heating in capillary rheometer cylinder, makes polymer balance five minutes (min) at 190 DEG C, and then with 2.54 This polymer is extruded through the capillary tube die of diameter 0.21cm and length 4.19cm by the piston speed of cm/min.Draw Power is preferably with being located so that roll leaves the Gao Tefu of 10cm immediately below the point of capillary tube die (Goettfert) at long filament Rheotens measures.
The melt strength of the EAO interpretation used in the practice of the present invention be usually 5cN or bigger, preferably 6cN or More greatly and more preferably 7cN or bigger or 8cN or bigger.In one embodiment, melt strength is that 5cN arrives 50cN, preferably 5cN to 35cN and more preferably 5cN to 20cN.All indivedual values of 5cN to 50cN All it is incorporated herein with subrange and is disclosed in herein.
Preferably, the molecular weight distribution (MWD) of the EAO interpretation used in the practice of the present invention is 1.5 to 4.5, More preferably 1.8 to 3.8 and most preferably 2.0 to 3.4.All indivedual values of 1.5 to 4.5 and subrange are all included In this article and be disclosed in herein.Many is applicable to the EAO interpretation of present invention practice can be by being described in USP Prepared by the method in 6,680,361.
In another embodiment, the density of EAO interpretation is 0.84g/cc to 0.92g/cc, preferably 0.85g/cc To 0.89g/cc and more preferably 0.85g/cc to 0.88g/cc.All indivedual values of 0.84g/cc to 0.92g/cc and Subrange is all incorporated herein and is disclosed in herein.
In another embodiment, the melt index (MI) I2 (190 DEG C/2.16kg) of EAO interpretation is 0.05g/10min To 10g/10min, preferably 0.1g/10min to 5g/10min and more preferably 0.2g/10min to 2g/10min Or 0.5g/10min to 1g/10min.All indivedual values of 0.05g/10min to 10g/10min and subrange all by It is included herein and is disclosed in herein.In another embodiment, the melt index (MI) I2 of elastomeric component is 2g/10 Min or less.
Preferably, in terms of the gross weight of elastic composition, EAO component is with equal to or less than 70 weight %, preferably etc. In or be present in the elastic composition of the present invention less than the amount of 60 weight %.
Preferably, in terms of the gross weight of elastic composition, EAO component is with equal to or more than 40 weight %, preferably etc. In or be present in the elastic composition of the present invention more than the amount of 50 weight %.
Component (b) in the elastic composition of the present invention is very low density polyethylene.The terms " extra-low density Polyethylene " or " VLDPE " be used for describing linear ethylene/alpha olefin copolymer, described linear ethylene/alpha olefin copolymer Density typically between about 0.86 and 0.915 gram/cc (g/cc), more preferably at about 0.883g/cc to 0.911 Between g/cc, more preferably less than 0.89g/cc." ultra-low density polyethylene " or ULDPE are also included within this term.
VLDPE ethylene/alpha-olefin polymer for the present invention can use Ziegler-type in conventional gas phase polymerization method (Ziegler-type) prepared by catalyst (such as zirconium, titanium and vanadium catalyst system).VLDPE polymer for the present invention The ethene polymers of the well-known substantial linear not being polymerized with use metallocene catalyst system and/or linear ethylene Polymer (S/LEP) is obscured.Can be used for propylene polymerization polymer blends to prepare the thermoplastic elastic composition of the present invention VLDPE is ethene polymers, and described ethene polymers does not have uniform chain branching, but has uneven chain and prop up Change.The most branched ethylene/alpha-olefin polymer (S/LEP) and it is with uneven ethylene/alpha-olefin polymer (VLDPE) Difference be well-known and be described in USP 6,184,290；6,184,291；6,218,470；6,369,161；With And 6, in 403,710, entire contents is incorporated herein.
Suitably VLDPE polymer is the copolymer of ethylene and alpha-olefin.Preferred VLDPE used herein is high Polydispersity polymer, it is at room temperature generally rigidity, but can easily shape when heated.Contain in the copolymer Alpha-olefin is selected from propylene, 1-butylene, 1-hexene, 1-octene and the group of senior 1-alkene and with at least 5 weight %, excellent Select 10 weight % or more greatly and more preferably 20 weight % or bigger concentration exist.
The preferred melt flow rate (MFR) (MFR) (being sometimes referred to as melt index (MI) (MI)) of VLDPE ethylene/alpha-olefin copolymer Being about 0.05 to 5.0 grams/10 minutes (g/10min), according to ASTM D 1238, (condition: 190 DEG C, 2.16 thousand Gram load under (190 DEG C/2.16kg)) measure.The MFR of the VLDPE in the present composition is preferably equal to Or greater than about 0.05g/10min, more preferably equal to or greater than about 0.12g/10min, and more preferably equal to or greater than about 0.15g/10min.The MFR of the VLDPE in the present composition is preferably equal to or smaller than about 5g/10min, More preferably equal to or less than about 2g/10min, more preferably equal to or less than about 1g/10min, and be more preferably equal to or little In about 0.5g/10min.
The density of the VLDPE in elastic composition of the present invention equals to or less than 0.915g/cc, is preferably equal to or little In 0.911g/cc and more preferably equal to or less than 0.89g/cc.VLDPE's in elastic composition of the present invention Density equal to or more than 0.86g/cc, more preferably equal to or greater than 0.883g/cc and even more preferably equals to or more than 0.886g/cc。
Preferably VLDPE polymer features is high molecular (the most relatively low melt index (MI)), wide molecular weight distribution (the most of a relatively high flow rate ratio) and relatively low degree of crystallinity.They are characterized as being further has about-52 DEG C and arrives Glass transition temperature between-39 DEG C, the Shore A hardness of about 77 to 95, peak value between 114 DEG C to 119 DEG C The bending modulus of melting range and about 30MPa to 1500MPa.
It is suitable for the melt tan δ of VLDPE of the present invention equal to or more than 0.7, preferably equal to or greater than 0.8 and more excellent Choosing equal to or more than 0.9, as by parallel-plate rheometer under 0.1 radian per second (rad/sec), 180 DEG C and 10% strain Measured.It is suitable for the melt tan δ of VLDPE of the present invention equal to or less than 8, preferably equal to or smaller than 5, more excellent Choosing is equal to or less than 2.5, as measured by by parallel-plate rheometer under 0.1rad/sec, 180 DEG C and 10% strain.
In one embodiment, as used the ARES rheometer with EVF stretching attachment on compression molded specimens At 190 DEG C and 1.0sec-1Strain rate is lower to be measured, the tensile viscosity etc. of the VLDPE component being suitable in the present invention In or more than 200,000Pa-s, more preferably equal to or greater than 300,000Pa-s and most preferably equal to or greater than 400,000 Pa-s, measures under straining at the Hencky of 2.5cm/cm.
Preferably, in terms of the gross weight of elastic composition, VLDPE component is with equal to or more than 5 weight % and preferably It is present in elastic composition equal to or more than the amount of 10 weight %.
Preferably, in terms of the gross weight of elastic composition, VLDPE component is with equal to or less than 30 weight % and excellent Choosing is present in elastic composition equal to or less than the amount of 20 weight %.
The propylene polymer component (c) of the elastic composition of the present invention comprises at least one branched polypropylene homopolymer or extremely Few a kind of branched polypropylene interpretation.Other suitable acronal includes the branched common of propylene and at least one alpha-olefin Polymers；Or branched homopolymer and/or the blend of branched copolymers；And/or nucleation homopolymer, nucleation copolymer or branched The nucleation blend of homopolymer and branched copolymers.
Propylene polymer component can be branched p 0 lypropylene and unbranched polyacrylic mixture, wherein with propylene polymer component Weight meter, branched p 0 lypropylene exists with the amount of at least 10 weight %, in terms of the weight of propylene polymer component, the most extremely Few 20 weight %, more preferably at least 30 weight %, more preferably at least 40 weight %, more preferably at least 50 weight %, more Preferably at least 60 weight %, more preferably at least 70 weight %, more preferably at least 80 weight % and most preferably at least 90 Weight %.
The branched p 0 lypropylene polymers compositions of the present invention can also comprise polypropene impact-resistant copolymer, and it is via azide Coupling and branched and/or rheology modified to provide the branched and/or polypropene impact-resistant copolymer of coupling.Polypropene impact-resistant Copolymer can be prepared as described in WO 01/58970, and described patent is incorporated herein in entirety by reference.'970 List of references describe that reactor produces containing Noblen or the Propylene impact copolymers of copolymer, with containing 20 Weight % is to the propylene copolymer of ethylene, butylene, hexane and/or the octene co-monomer of 70 weight %.
By radiation (such as electron beam or gamma-radiation) in the case of suitably branched p 0 lypropylene is additionally included in presence or absence adjuvant Branched and/or the polypropylene of coupling formed.This type of branching reaction is carried out the most in an inert atmosphere.
Other suitable polyacrylic polymer includes that, as being described in USP 6, the coupling polymer in 552,129, it is in full The mode quoted is incorporated herein.As at USP 6, described in 552,129, poly-(sulfonyl azide) coupling polymer by with Lower step is formed: (a) forms the first polymer and first admixture of poly-(sulfonyl azide)；B () then forms first and mixes Second admixture of at least one the second polymer of compound and the second amount；(c) the second admixture is heated at least to The decomposition temperature of coupling agent, maintains and be enough to make the time of polymer chain coupling.Additional acrylic polymers can be by product Or at least one poly-(sulfonyl azide) and acronal of at least one vinyl elastomer of blend product, coupling amount Formed.
As used herein, " branched p 0 lypropylene ", " branched polypropylene homopolymer ", " propylene and one or more α- The branched copolymers of alkene " or similar terms mean containing one or more H types or T-shaped branched polypropylene, H type and T-shaped branched discussing fully can be found in the USP 8,304,496 that full content is incorporated herein.In short, generally In the presence of the catalyst (metallocene-type or single site catalysts) of constrained geometry configuration, suitable reactor condition (as Described in WO 00/26268 (US equivalent USP 6,680,361, it is incorporated herein in entirety by reference) Those conditions) under, obtain T-shaped by the combined polymerization of ethylene or other alpha-olefin with end of the chain unsaturated macromers Change.Generally by ethylene or other alpha-olefin with have can be with two of the Nonmetallocene type catalyst reaction in polymerization It is branched that the combined polymerization of the diene of double bond obtains H type.As the name implies, diene passes through diene bridging by a polymer Molecule is connected to another polymer molecule, and resulting polymers molecule is similar to H, can be described as more cross-linking than long chain branches. When expecting high level branched, generally use H type branched.When using H type branching agent, the catalysis used Agent is frequently not metallocene catalyst.USP 6,372,847 (being incorporated herein in entirety by reference) is used for preparing The catalyst of H type branched polymer is vanadium type catalyst.Lai et al. describes T-shaped long-chain in USP 5,272,236 and props up Changing (LCB) polymer, wherein the degree of LCB is that 0.01LCB/1000 carbon atom to 3LCB/1000 carbon is former Son and the catalyst (metallocene-type or single site catalysts) that catalyst is constrained geometry configuration.
There is the isotactic polypropylene homopolymer of LCB or example that copolymer is T-shaped branched p 0 lypropylene.There is H type Branched branched p 0 lypropylene can use the reactive extrursion as described in USP 6,472,473 and 6,841,620 or such as USP Irradiation described in 5,514,761 prepares.Being incorporated herein the most in entirety by reference in these three patent.
Suitably branched p 0 lypropylene also includes the polymer containing the polyethylene branch being incorporated in polypropylene backbone, as to draw The USP 6,750,307 that is incorporated herein of mode described in.Herein, there is isotactic polypropylene main chain Branched olefin copolymers contains polyethylene branch and optionally one or more comonomers.Generally, branched olefin copolymers Total comonomer content be 0 to 20 moles of %.It addition, the mass ratio of isotactic polypropylene and polyethylene generally exists In the range of 99.9:0.1 to 50:50.This type of branched polypropylene copolymer can be such as USP 6, described in 750,307, by following Prepared by step: a) under conditions of being enough to form the copolymer having more than 40% terminated radical degree of unsaturation, make ethylene Optionally with the combined polymerization in the polymerization of one or more copolymerisable monomers；B) in polymer reactor, suitably Under the conditions of polypropylene polymerization, use and can prepare the chirality of isotactic polypropylene, solid rigid transition-metal catalyst, Make product a) and propylene and optionally one or more copolymerisable monomer combined polymerizations；And c) reclaim branched olefin altogether Polymers.
Alpha-olefin in branched polypropylene copolymer is preferably ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene Or 4-methyl-1-pentene, wherein ethylene is preferred.Alpha-olefin in propylene copolymer is preferably ethylene.Copolymer can For random copolymer or block copolymer or random copolymer and the blend of block copolymer.
The MFR (230 DEG C/2.16kg weight) of the propylene component of blend polymer is preferably 0.1g/10min to 150 G/10min, preferably 0.3g/10min to 60g/10min, more preferably 0.4g/10min to 40g/10min, very To more preferably 0.5g/10min to 25g/10min, more preferably 1g/10min to 20g/10min and most preferably For 2g/10min to 15g/10min.All indivedual values of 0.1g/10min to 150g/10min and subrange are all wrapped Include in this article and be disclosed in herein.This component has the fusing point more than 145 DEG C the most ideally.Real at another Executing in example, the fusing point (Tm) of propylene component is 130 DEG C to 180 DEG C, preferably 140 DEG C to 170 DEG C.□
In another embodiment, the MFR (230 DEG C/2.16kg weight) of branched p 0 lypropylene is 0.1g/10min to 150 G/10min, preferably 0.2g/10min to 40g/10min, more preferably 0.5g/10min to 30g/10min and Most preferably 0.5g/10min to 2g/10min.All indivedual values of 0.1g/10min to 150g/10min and sub-model Enclose and be all incorporated herein and be disclosed in herein.This component has the fusing point more than 145 DEG C the most ideally.
The melt tan δ of at least one branched polypropylene polymer equals to or less than 2, preferably equal to or smaller than 1.75, and more Preferably equal to or smaller than 1.5, as measured by by parallel-plate rheometer under 0.1rad/sec, 180 DEG C and 10% strain. Preferably, the ratio of the melt tan δ of VLDPE and the melt tan δ of polypropylene component is 0.1 to 4, and preferably 0.5 arrives 2。
As used herein, " nucleation " refers to by adding nucleator (such as MILLADTM, it is purchased from Milliken (Milliken) benzhydryl sorbitol) modified polymer.It is used as the nucleator of other routine.
The preparation of branched p 0 lypropylene can relate to Ziegler catalyst, such as titanous chloride. and making that diethyl monochlor(in)ate aluminum combines With, as by Cecchin at USP 4, described in 177,160, it is incorporated herein in entirety by reference.For making The polymerization of this type of high molten polymer includes slurry method (it is at about 50 DEG C to 90 DEG C and 0.5MPa to 1.5 Perform under MPa (5 atmospheric pressure (atm) to 15atm)) and gas phase and liquid monomer method, wherein must give Give additional attention to remove amorphous polymer.Alpha olefin copolymer can add in reaction to form block copolymer.Poly- Propylene also by use multiple metallocene, unit point and any one in the catalyst of constrained geometry configuration and its associate Method prepare.
Suitably branched p 0 lypropylene includes the PROFAX being purchased from Basel (Basell)TMBranched p 0 lypropylene, from north The DAPLOY of europeanized work (Borealis)TMWith the INSPIRE from Blasco (Braskem)TM。
Preferably, in terms of the gross weight of elastic composition, propylene polymer component is with equal to or less than 40 weight %, excellent Choosing is present in the elastic composition of the present invention equal to or less than the amount of 30 weight %.
Preferably, in terms of the gross weight of elastic composition, propylene polymer component is with equal to or more than 10 weight %, excellent Choosing is present in the elastic composition of the present invention equal to or more than the amount of 20 weight %.
Additionally, the elastic composition of the present invention advantageously can further include at least one add to routinely elastomer gather The additive of the type in polymer composition.These additives include such as processing oil；Antioxidant, preferred hindered phenol Antioxidant is IRGANOXTM1010 and IRGANOX 1076 antioxidant or organic phosphates, as IRGAFOSTM168 (being entirely purchased from vapour Ba-Jia Ji company (Ciba-Geigy Corporation))；Surface tension modifier； UV stabilizer；Scratch/scratch additive, such as polydimethylsiloxane (PDMS) or the polydimethylsiloxanes of functionalization Alkane or the scraping composite containing erucyl amide；Anticaking agent；Dispersant；Foaming agent；Linear or the second of substantial linear Alkene polymer；LDPE；LLDPE；Lubricant；Cross-linking agent, such as peroxide；Antibacterial, such as Organometallic compounds Thing, isothiazolone, organic sulfur and mercaptan；Antioxidant, such as phenolic resin, secondary amine, phosphite ester and thioesters；Anti-quiet Electricity agent, such as quaternary ammonium compound, amine and ethoxylation, propoxylation or glycerol compounds；Filler and hardening agent, such as silicon Lime stone, carbon black, glass, metal carbonate (such as calcium carbonate), metal sulfate (such as calcium sulfate), Talcum, clay, Muscovitum or graphite fibre.
Additional additives includes hydrolysis stabilizer；Lubricant, such as fatty acid, fatty alcohol, ester, fatty acid amide, stearic acid Slaine, paraffin and microwax, silicone and orthophosphate；Releasing agent, as fine particle or pulverulent solids, soap, Wax, silicone, polyglycols and mixed ester (such as trimethylolpropane tris stearic acid ester or pentaerythritol tetrastearate)；Face Material, dyes and dyestuffs；Plasticiser, such as the ester of binary acid (or its anhydride) Yu monohydric alcohol, as phthalic acid ester, Adipate ester and benzoate；Heat stabilizer, such as organo-tin mercaptide, thioglycolic acid monooctyl ester and barium formate or formic acid cadmium； The UV light stabilizing agent used, such as hindered amine, adjacent hydroxy-pheny benzotriazole, 2-hydroxyl, 4-alkoxy benzophenone, Salicylate, cyanoacrylate, nickel chelating agen and toluenyl malonic ester and oxanilide；And zeolite, molecular sieve, Antistatic additive and deodorizer known to other.
Those skilled in the art are readily able to select the combination of any suitable additive and additive capacity and by additive also Enter the method in compositions without too much experiment.With general composition weight meter, every kind in above additive (if made With) typically not greater than 45 weight %, and advantageously it is about 0.001 weight % to about 20 weight %, it is therefore preferable to 0.01 Weight % is to 15 weight % and more preferably 0.1 weight % to 10 weight %.
Using the extrusion of any routine, be blow molded, foam or thermo shaping method, elastic composition of the present invention may be produced that portion Part, sheet material or other goods.The instantiation of this type of method includes sheet material extrusion, section bar extrusion, blowing and hot forming, Particularly vacuum-thermoform.This type of method can prepare goods or the product with smooth or embossed surface.
The elastic composition of the present invention can by by one or more ethylene/alpha-olefins (EAO), one or more VLDPE is prepared with the combination of one or more branched p 0 lypropylenes.Although such composition can be by many distinct methods Any one prepare, but these methods are generally after the one in two categories below, i.e. reactor and are blended and are blended in reactor. The former illustrative example is for being fed to two or more solid polymers wherein and physical mixed becomes the most equal The melt extruder of even compositions, and press multiple solution reactors, slurry phase reactor or the gas phase that parallel connected array is arranged Reactor, and wherein blended to form substantially uniform compositions each other from the output of each reactor, described Compositions is finally with in recovered in solid form.The illustrative example of the latter is multiple reactor being connected in series and equipped with two kinds Or the single reactor of more kinds of catalyst.
Can extruder, wheel press, blow machine, foaming machine or melt blended material and prepare manufacture goods other Carrying out in the former of kind mixing or melt blending, this is sometimes referred to as tandem mixture.Alternately, the present invention Elastomeric polymer composition can extrude melt blending by conventional, wherein obtains the change with or without additive Compound (being typically pellet form).Then, gained compound (or pill) is extruded into sheet material, section bar, blowing system Product, injection-molded item or hot forming.During pure additive can add mixture to, in other words with its standard conditions (that is, as Liquid and/or powder), such as concentrate and/or masterbatch.
Before manufacturing goods, compositions also can be blended with another kind of polymer.This type of is blended can pass through multiple routine techniques In any one carry out, one of which is that dry type is blended the pill of prolylene polymer composition of the present invention and another kind of polymer Pill.
The elastic composition of the present invention can be additionally used in extrusion-blown modling method to form extrusion-blow molding product.
In a preferred embodiment, the elastic composition of the present invention is in the method preparing automobile product.Manufacture this type of system A kind of method of product is for being initially formed sheet material, and for example extrusion sheet, optionally embossed sheet (that is, has veining Or the sheet material of " yarn face " outward appearance, wherein when preparing sheet material, veining can be at identical (on line) or different (under line) Step is carried out).The thickness of sheet material is preferably equal to or greater than 0.5mm, more preferably equal to or greater than 0.6mm and even More preferably equal to or greater than 0.7mm.The thickness of sheet material is preferably equal to or smaller than 4.0mm, more preferably equal to or less than 3mm And even more preferably equal to or less than 2mm.Then, (it is sometimes referred to as " positive " by hot forming, forward hot forming Hot forming) or preferably negative sense hot forming (being sometimes referred to as " cloudy " hot forming), it is that formed automobile goods are (excellent by sheet forming The floor do not carpeted of choosing) shape.By sheet material and/or hot forming floor applications in vehicle interior floor.Meet desirably Any thickness that plate requires is acceptable；Preferably sheet thickness be at least 3mm, more preferably thickness be 2mm.
In another embodiment of the present invention, elastic composition can be AB type with suitable thermoplastic coextrusion The cover layer (wherein the elastic composition of the present invention is A layer) of sheet material or for trilaminate (such as, ABA type Sheet material, wherein the elastic composition of the present invention is A layer), thus the wearability of improvement and relatively low glossiness are provided. The elastic composition of the present invention is coextruded on any thermoplastic being suitable for sound and vibration elimination, for example Comprise following in the acoustic barrier of one or more and/or vibration control compositions: EVA, EPDM, ethylene-alpha-olefin Copolymer, ethylene-olefin block copolymer and the analog being filled with calcium carbonate, barium sulfate and combinations thereof.
The thickness of cover layer (the A layer of AB matrix material and/or the A layer of ABA type sheet material) is preferably equal to or greater than 0.2mm, It is more preferably equal to or greater than 0.4mm and even more preferably equal to or more than 0.5mm.The thickness of cover layer is preferably equal to Or less than 2mm, more preferably equal to or less than 1.5mm, even more preferably equal to or less than 1mm and the most excellent Choosing is equal to or less than 0.8mm.
Preferably equal to or less than 220 DEG C, more preferably equal to or less than 200 DEG C, more preferably equal to or less than 190 DEG C, and And at a temperature of most preferably equal to or less than 180 DEG C, perform hot forming.Preferably equal to or more than 130 DEG C, more preferably etc. In or more than performing hot forming at a temperature of 140 DEG C and more preferably equal to or greater than 150 DEG C.This is comprised for hot forming The selected objective target temperature of the sheet material of the elastic composition of invention is 160 DEG C.
Melt tan δ is in order to judge that particular thermal plastic composition has many applicable hot formed useful parameters.Melt tan δ is If the viscous modulus measured on dynamical mechanical spectrometer in molten state is divided by the ratio (G "/G') of elastic modelling quantity.If should Value height, then sample is readily flowed and has little melt strength.If this value is low, then sample has substantial amounts of bullet Property memory or store energy and little fluid ability.Preferably, thermoplastic compounds has enough melt strengths to avoid In hot forming baking oven sagging too much, but when around instrument by vacuum drawing part, still there is certain fluid ability. Material can have excessive melt strength and too small melt strength.Generally, when particular thermal plastic composition is in suitably warm When melt tan δ in the range of forming temperature is between 1 to 2, suitable hot forming melt strength can be found.
Example
Example 1 arrives example 3 and comparative example A with comparative example B at 1.25 inches of (in) sheet extruders of Killion Upper use has the barrier screw of Maddock blender and carries out melt blending and be extruded into sheet material.All components is in charging Before in extruder, upset is blended 20 minutes.The sheet material that size about 1mm is thick and 10in is wide is expressed into there is chromium throwing On one group of Davis Standard tri-roller of light steel rider.Extruder barrel temperature from hopper to mould is 195 DEG C, 200 DEG C, 210 DEG C, 215 DEG C and 215 DEG C and the melt temperature of 240 DEG C and roller group temperature from the top to the bottom are 32 DEG C, 32 DEG C With 23 DEG C.□
Example 1 to the composition of example 3 and comparative example A and comparative example B in table 1 below in terms of the gross weight of compositions Weight portion be given.Unless otherwise noted, otherwise molecular weight is exhausted for measured by Angle Laser Light Scatter (LALLS) Molecular weight and Mooney viscosity are measured according to ASTM D 1646.In Table 1:
" EAO-1 " is the interpretation that ethylene/propylene/diene is modified, and it has 70 weight % ethylene and 4.9 weight %5- Ethylidene-2-norborene, density is 0.88g/cc, the Mooney viscosity at 125 DEG C be 70ML (1+4) and MFR under 190 DEG C/2.16kg is about 0.1g/10min, can be with NORDELTM4770P is purchased from Dow Chemical；
" EAO-2 " is the interpretation that ethylene/propylene/diene is modified, and it has 67 weight % ethylene and 2.2 weight %5-are sub- Ethyl-2-norborene, density is 0.88g/cc, and the Mooney viscosity at 125 DEG C is 60ML (1+4) and 190 DEG C/2.16 MFR under kg is about 0.1g/10min, can be with NORDEL 3760P purchased from Dow Chemical；
" EAO-3 " is the interpretation that ethylene/propylene/diene is modified, and it has 71 weight % ethylene and 0.5 weight %5- Ethylidene-2-norborene, density is 0.88g/cc, and the Mooney viscosity at 125 DEG C is 18ML (1+4), and weight average divides Son amount (Mw) about 120,000 and molecular weight distribution are about 7, can be public purchased from DOW Chemical with NORDEL 3722P Department；
" EAO-4 " is the interpretation that ethylene/propylene/diene is modified, and it has 70 weight % ethylene and 0.6 weight %5-is sub- Ethyl-2-norborene, density is 0.867g/cc, and the Mooney viscosity at 125 DEG C is 20ML (1+4), 190 DEG C/2.16 MFR under kg is about 1g/10min, and weight average molecular weight (Mw) is about 114,800, and number-average molecular weight (Mn) is about 28,350 and molecular weight distribution (Mw/Mn) be about 4.05, can be with NORDEL 3720P purchased from Dow Chemical；
" VLDPE " for use metallocene (Ziegler Nada) catalyst via gas-phase polymerization prepare extremely low close Degree polyethylene, it is ethylene-butene copolymer, it is characterised in that MFR (190 DEG C/2.16kg) is 0.1g/10min, Density is 0.884g/cc, as at 200 DEG C and 120sec-1Under be 2415Pa-s by the viscosity of capillary rheometer determining, Rheology ratio is 30, and Shore D level hardness is 29；And weight average molecular weight is 250,000 gram/mol (g/mol), z Average molecular weight is 920,000g/mol, can be with ENGAGETMHM 7280 is purchased from Dow Chemical；
" PP-1 " is branched polypropylene-ethylene copolymer, and it has 8.5% ethylene, and MFR (230 DEG C/2.16kg) is 0.5 G/10min, density is 0.903g/cc, and as at 200 DEG C and 120sec-1Under viscous by capillary rheometer determining Degree is 430,000g/mol for 1400Pa-s and weight average molecular weight (Mw), can be with D114 purchased from Dow Chemical；
" PP-2 " is nucleation highly crystalline Noblen, and its number-average molecular weight (Mn) is 41,000g/mol, weight average MW is 183,000g/mol and Mn/MW is about 4.5, can be with D114 purchased from Dow Chemical；
And
" Black ", can be with K-6807-Q purchased from the triumphant public affairs of U.S.'s Aomei for comprise carbon black black concentrate in polypropylene Department (Americhem).
Characterize and test below example 1 to example 3 and comparative example A and comparative example B are performed:
" modulus " is according to ASTM D747,3 the apparent bending moduluses measured parallel and perpendicular to extrusion direction And it is reported as MPa；
" 60 ° of Gardner (Gardner) glossiness " measures according to ASTM D523, and numerical value is reported with %；
" Taibo abrasion (Taber Abrasion) " recycles H-18 wheel with 500 times, surveys according to ASTM D4060 Fixed；And
" scratch albefaction (Scuff Whitening) " measures according to ASTM D6279, by the equal interval scale of 1 to 5 Assessment performance, the highest scratch/albefaction obtains higher grade.
Table 1

Claims (8)

1. an elastic composition, it comprises:
A) measuring the interpretation of the ethylene/alpha-olefin/diene modification being 40 weight portions to 60 weight portions, it has 0.84g/cc To the density of 0.92g/cc and at 125 DEG C, equal to or more than 50ML (1+4) such as measure according to ASTM D 1646 Mooney viscosity；
B) amount is the extra-low density ethylene polymers compositions of 10 weight portions to 20 weight portions, and its density equals to or less than 0.89g/cc；
And
C) amount is 20 weight portions propylene polymer component to 30 weight portions, and it comprises at least one branched p 0 lypropylene.
Compositions the most according to claim 1, the interpretation that wherein said ethylene/alpha-olefin/diene is modified described Diene is 5-ethylidene-2-norbornene；1,4-hexadiene；Or 7-methyl isophthalic acid, 6-octadiene.
Compositions the most according to claim 1, at least one branched p 0 lypropylene wherein said is propylene and alpha-olefin Copolymer, described alpha-olefin is selected from ethylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene or 1-octene.
Compositions the most according to claim 1, wherein said propylene polymer component is branched p 0 lypropylene and unbranched Polyacrylic mixture.
Compositions the most according to claim 3, wherein in terms of the weight of described propylene polymer component, described branched Polypropylene exists with at least 50 weight %.
6. preparing an automobile method with the floor do not carpeted, it comprises the steps of
I) forming the sheet material comprising elastic composition, described elastic composition comprises:
A) measuring the interpretation of the ethylene/alpha-olefin/diene modification being 40 weight portions to 60 weight portions, it has 0.84g/cc To the density of 0.92g/cc and at 125 DEG C, equal to or more than 50ML (1+4) such as measure according to ASTM D 1646 Mooney viscosity；
B) amount is the extra-low density ethylene polymers compositions of 10 weight portions to 20 weight portions, and its density equals to or less than 0.89g/cc；
And
C) amount is 20 weight portions propylene polymer component to 30 weight portions, and it comprises at least one branched p 0 lypropylene And
Ii) described sheet material is thermoformed into the automobile floor do not carpeted.
Method the most according to claim 6, wherein said sheet material is AB type coextrusion sheet material or ABA type co-extrusion Going out sheet material, the wherein said elastomer compositions that comprises is A layer.
8. the automobile floor do not carpeted, it is prepared by the method described in claim 6 or 7.
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